-1- Introduction The high intertidal gastropod Littorina planaxis excretes a variety of nitrogenous waste products (Campbell, 1970; Cox, 1964; Duerr, 1968; Needham, 1938). In the kidney, ammonia is the predominant non-protein nitrogenous waste product (Campbell, 1970; Cox, 1964). Cox found evidence of a tidal rhythmicity in the amount of ammonia found in the kidney. The highest concentrations of ammonia were found during the ascending tides. After this point, the amount decreased, reaching a minimum value at low tide. While small amounts of ammonia may be liberated as gas when the animals are dry (Lebenzon, 1964), Duerr (1968) found that several species of marine prosobranch molluscs, including Littorina sitkana, excrete ammonia in solution upon being immersed. Immersion may stimulate excretion. Kops (1964) found that moisture was a stimulus to activity. While Kops found no evidence of a circadian effect on activity, observations indicate that physical activity does increase at night, and an in¬ crease in metabolic and/or excretory activity may parallel this increase. If moisture is indeed a stimulus for ac¬ tivity and for excretion, L. planaxis may be exploiting two periods of high moisture. The rocky substrate on which it lives is moistened by the splash of the high tide and by dew which condenses during the night. Fluc¬ tuations in ammonia excretion during the tidal and diurnal -2- cycles are the focus of the study reported here. Materials and Methods Snails were collected from the rocky intertidal at the Hopkins Marine Station, Pacific Grove, California. The vertical range of the collecting site was 8 to 12 feet above mean lower low water. Ammonia was collected from five replicates of ten snails each, which were placed in 250 ml. beakers with 5 ml. sea water and swirled, to wet the snails thoroughly. After one hour, the beakers were swirled again to mix the sample, the snails were removed, and the water was centrifuged to remove fecal material. One ml. aliquots were removed and tested for the presence of ammonia using a colorimetric proceedure (Ternberg and Hershey, 1964). After color development, centrifugation was necessary to remove precipitated carbonates. Samples were read in a Gilson 252 Spectrophotometer at 625 nm, against a distilled water blank, and corrected for any ammonia present in the sea water used for collecting ammonia. Duerr (1968) found a correlation between the amount of ammonia excreted and the total weight of the animal. The amounts of excreted ammonia were normalized by dividing by the weight of the snails sampled, and expressed as ug ammonia/ g snail. Results The fluctuations in ammonia excretion by animals during the tidal and diurnal cycles were studied as follows. Snails were collected from the field at the high and low tides and at times intermediate between these extreme points. Snails were brought into the laboratory and tested within fifteen minutes. Figure 1 shows the results of this study. Note the wide range of amounts of ammonia excreted at different times. Individual values range from .65 to 3.05 ug NH3/ g snail, and the means range from 1.15 to 2.60 ug NH3/ g snail. The lowest individual value and the lowest mean value both occur during the day¬ time low tide, while the highest individual value and the highest mean value both occur at high tide after sunset. The lowest values obtained during the night, during the falling and low tides, have means 22% and 61% higher, respec¬ tively, than means for similar points on the tidal cycle during the day. During the night, excretory activity in¬ creases throughout the tidal cycle. A similar study was made using the same five groups of ten snails at each sample time in an attempt to decrease the variability observed in the previous study. Fifty snails were collected at 0900 hours, on the ascending tide. Between sampling times, the snails were left outside the laboratory, subjected to the normal diurnal regime, and brought into the laboratory only for testing. This ex¬ periment eliminated any tidal effect, because the snails were immersed every three hours. Figure 2 presents the results. Figure 3 shows the amount excreted by the in¬ dividual test groups. Again, the lowest values are obtained during the daylight hours; values rose as night approached and decreased again after sunrise. Variability did decrease; the 95% confidence intervals ranged from +.05 to +.50 ug NH3/ g snail, while the 95% confidence intervals for values obtained during the field study ranged from +.15 to +.90 Ug NH3/g snail. The snails excreted an average of 40% more ammonia the next morning, after twenty-four hours of periodic immersion. After the final test at 1400 hours, the snails were again placed outside and tested after twenty hours of dryness. The mean value, .03 ug NHa/g snail, decreased to the level obtained at the start of the first day, when the snails had been collected on a low tide. Since a period of dryness appears to depress excretory activity, the next study examined the effects of prolonged dryness, Figure 4. Four hundred snails were collected at 1330 hours, on the descending tide. The snails were kept in an open container outside, subject to the normal light regime, to normal temperature fluctuations and to deposition of dew, yet were removed from the beach area, eliminating any exogenous tidal influences. At every test time, fifty fresh snails were taken from the con¬ tainer and brought into the laboratory for testing. The -5 large rise in amount of ammonia excreted which was evi¬ dent in the previous two studies is not apparent. The range of means is much narrower, .65 to 1.10 ug NH3/g snail. The smallest 95% confidence interval occurs at the low tide, 1600 hours, only two hours after collection. As the tide rises, yet the period of dryness increases, var¬ iability increases, except for the point at 0830, on the ascending tide just after sunrise. The lowest mean occurs at 1200 hours, the final testing point, at the high tide. Under abnormal moisture conditions, the snails display a high degree of individual variability. Some may have been affected more by the lack of moisture and excreted less, or not at all. A fourth experiment, shown in Figures 5 and 6, ex¬ amined differences in excretory behavior between snails kept in constant light or constant dark. One hundred snails were collected from the field at 0900 hours, on the descending tide. Fifty snails, in five groups of ten each, were placed in constant dark and fifty were placed in constant light. The first sample was tested at 1100 hours, during the low tide, so that the snails in the dark had two hours to respond to the change in light conditions. The same ten groups, five in constant arti¬ ficial light and five in constant dark, were sampled at each test time. Both groups showed peaks of excretion at the high tide; the snails kept in constant light showed a larger difference in amplitude between day and night peaks than those kept in the dark. During hours of normal daylight, -6- the 95% confidence interval of snails kept in the light was similar to that of snails periodically immersed yet kept on a normal day/night cycle, see Figure 2. After the time of sunset, however, the 95% confidence intervals increased, becoming almost three times that of snails in Figure 2 at 0400 hours. The snails kept in constant dark had consistently larger confidence intervals than those of Figure 2, increasing up to 188% at 0000 hours. Again, under abnormal conditions, the snails display a greater degree of individual variability. Another set of investigations attempted to discover if any relationship exists between amounts of ammonia syn¬ thesized and time of day. At 1100 and 2100 hours, the standard sampling proceedure was followed, although sample size was increased to twenty snails and 10 ml. of sea water was used. At fifteen minute intervals, samples were withdrawn and fresh sea water was added to maintain a constant vol¬ ume. The values for subsequent readings were corrected for this dilution effect. Figure 7 shows the difference between two groups of snails, one from each testing period. Initially, the amounts of ammonia excreted by the two groups appear to be identical. However, during the night, amounts excreted increase more than during the day. Discussion The presence or absence of light seems to be the -7- major factor in determing how much ammonia L. planaxis excretes. However, in the absence of light and dark cues, the tidal correlations become more apparent. In Figure 1, this combined diel/tidal cycle is most obvious; since snails were collected from the field at every test point, they were subject to normal environmental conditions until just prior to testing, i.e., they experienced up to seven hours between times of maximum moisture at the high tides. The amounts of excreted ammonia decrease after sunrise, and the final amount at 0900 parallels the amount found at the same time on the previous day. This may indicate that uniformly low levels of ammonia are excreted during the morning hours; the possibility also exists that the snails collected at this time, which coincided with high tide, had already excreted on the rising tide or just prior to the peak of the tide. In contrast, the groups of snails which were immersed every three hours excreted larger amounts of ammonia on the second morning, Figures 2 and 3. In all cases, however the snails excreted less on the third morning, after twen¬ ty hours of dryness. Moisture does seem to stimulate the snails to excrete. All individuals exhibit a diurnal pat¬ tern of excretion; excretory activity increases after sunset and decreases after sunrise. Whether the absense of tidal correlations is due to periodic immersion or to the coincidence of evening with the high tide cannot be determined; repeated studies during as evening low tide might reveal the degree of tidal influence. The hypothesis that moisture is a stimulus to excrete is supported by the data shown in Figure 4. The values obtained at the first sample time, 1400 hours, are almost identical to those in Figure 1, from snails brought in from the field and tested at 1400 hours. However, these snails fail to show any large increase in the amount excreted, despite the onset of darkness. While mean values for snails taken from the field range from 1.15 to 2.60 Ug NHa/ g snail, the mean values for the snails which were kept dry only range from .65 to 1.30 ug NH3/g snail. The small 95% confidence interval at 1600 hours, during low tide, may be due to the fact that, at this time, experimental conditions most nearly paralleled conditions in the field. As the tide rises, yet the snails exper¬ ience no increase in moisture, there is no large increase in mean values, while 95% confidence intervals increase. The snails are differentially affected by the absence of moisture. The interval is again small at 0830 hours; this test period occurs after sunrise, on the ascending tide. Moisture from dew had been observed in the container; perhaps, if the snails are indeed on a tidal cycle, this moisture signifies an incoming tide to some, which, an¬ ticipating a return of normal conditions, begin to excrete at a normal level. The mean value here, 1.20 +.20 ug NH./ g snail, is quite similar to that found in the field study at 0830, 1.20 +.45 ug NH3/g snail. The value at 1200 -9 decreased, however, despite the occurrence of high tide; two factors may account for this. Firstly, a similarly low level of excretory activity is displayed by snails taken from the field, in Figures 2 and 5; however, these low levels coincide with the low tide. Secondly, if the above hypothesis describing dew as a false moisture cue is correct, many of the snails may have excreted during what they assumed would be an ascending tide; yet, at high tide, when no moisture was forthcoming, some did not excrete, or excreted less. Such a conjecture is sup¬ ported by the findings graphed in Figures 2 and 3, where snails kept dry for twenty hours after twenty-eight hours of testing excreted less than they had at the same time on the previous day. Due to the large confidence inter¬ vals and the small range of means, Figure 4 does not in¬ dicate that any appreciable correlation exists between the amount excreted and either light or tidal conditions. While a large measure of variability may be due to dif¬ ferences among the five groups, i.e., different groups of fifty snails were tested at each dampling time, this graph may also indicate that, deprived of moisture, L. planaxis has less ammonia available to excrete. If the snails are given what appears to be an op¬ portunity to continue to make and excrete ammonia, i.e., if they are periodically immersed as those in Figures 2 and 3 were, test conditions of constant light and constant dark might obliterate the diurnal correlations observed -10- in Figures 2 and 3. In Figure 5, the mean values of both the groups kept in constant light and those kept in constant dark parallel the tidal cycle. The smaller amplitude of the daytime peak of the snails kept in constant light is consistent with results indicating that less ammonia is excreted during the day. The maxi¬ mum nighttime values, at the peak of high tide, are al¬ most identical to those of snails kept in constant dark¬ ness, and are greater than those obtained from the snails described in Figure 2. This suggests that, at least during the first day of constant light, an endogenous rhythmicity in excretory activity is not damped out. The snails are perhaps differentially affected by the abnormal conditions, however; while these five groups has 95% confidence inter¬ vals of +.20 to +.40 ug NH3/ g snail during normal hours of daylight, the confidence intervals increase to +.65 to +1.10 ug NHa/ g snail after the time of sunset. The snails placed in constant darkness always displayed high variability; once more, some may have been affected more than others by the abnormal conditions. The constant dark groups, also paralleling the tidal cycle, gave higher values during daylight hours than the snails kept in con¬ stant light; the artificial onset of darkness seems to be a cue to increase ammonia excretion. Following the patterns of individual groups, Figure 6, groups 1-8 parallel both tidal cycles. The constant light groups 3, 4 and 5 -11- seem to anticipate the high tide which occurs at sunrise. Two possible explanations of this behavior exist. The snails, deprived of normal light/dark cues, may have mis¬ calculated the time of high tide; since high tide occured at sunrise, the snails would be expected to excrete rela¬ tively large amounts at the onset of light, yet they receive no change in light conditions which might cue their response. On the other hand, prior to this time, none of the groups excrete large amounts which would normally be excreted during hours of darkness; perhaps they are storing ammonia until internal concentrations reach levels which they can no longer tolerate, and they excrete, regardless of time of day or point in the tidal cycle. The constant dark groups 9 and 10 did not show an increase and decrease in values during the daytime high tide. Per¬ haps the sudden advent of darkness failed to elicit the increase in amount excreted observed in the other two groups. Note, however, that sunset coincides with the falling tide on this day; the snails may have been res¬ ponding to what appeared to be sunset, and excreted smaller amounts of ammonia until the tide began to rise, after 0300 hours. The premature onset of darkness does not, however, seem to affect the tidal pattern of excretion beyond the first tidal cycle. Further investigations of levels of excretory activity under prolonged constant light and constant dark regimes might elucidate the nature -12- of this excretory rhythmicity, i.e., whether it is truly endogenous or rather a response to external conditions, Thus, while light conditions appear to be the strongest factor influencing ammonia excretion, the absence of light and dark cues make tidal correlations more apparent. Given the high intertidal habitat of L. planaxis, which has a vertical distribution of 5 to 12 feet above mean lower low water (Peterson, 1964), night appears to be a more reliable moisture cue; while dew is usually deposited on the rocks after dark, the snails may not always be splashed by the high tide, depending in their position on the rocks and the height of the surf. Note that, while in previous tests, Figures 2,3 and 4, the absence of moisture seems to inhibit ammonia excretion, the periodic wetting of the snails, which eliminates normal tidal cues, does not appear to damp out variations in levels of excretion apparently correlated with the tide. Cox (1964) found the lowest amount of ammonia in the kid¬ neys at lower low water, the period of maximum dryness; this finding corroborates the results which indicate that snails which are kept dry excrete less ammonia. Perhaps moisture is not only a stimulus for excretion, but, under conditions of periodic moisture, the snail has more ammonia available to excrete. Cox also found that the kidneys contained the greatest amount of ammonia on the ascending tide. The snails have been shown to excrete the largest amounts of ammonia on the ascending and high -13 tides. If the ammonia synthesized and stored in the kidney were excreted during this period, the amount in the kidney would be less at high tide than during the ascending tide. Moisture would facilitate ammonia excretion, since ammonia is soluble in water. Because large concentrations of ammonia are toxic, storing quantities of ammonia for extended periods of time might be harmful to the animal; thus the snails have ammonia available to excrete only during those times at which they are assured of the avail¬ ability of moisture, i.e., at night, when dew falls, and at the high tides. This hypothesis indicated that rates of synthesis, as well as amounts of available excretory products, may vary. Preliminary studies found that, over a four hour period of testing, the test water contained increasing amounts of ammonia for the first one to two hours, yet, after two hours, the concentration of ammonia in the test water remained fairly constant during the day. However, during the night, the concentration of ammonia in the test water increased over the entire four hour test period. During the day, the snails, in the first one to two hours of immersion, may have excreted any ammonia which they had accumulated. After this point, levels of excretory products would increase only slightly, if at all, if the rate of synthesis is low. At night, however, the amount excreted would continue to increase to a greater extent if the rate of synthesis is appreciably higher. Figure 7 gives data -14- for two different groups of twenty snails each, one tested during the morning and the other tested in the evening, while kept in constant dark. These two groups show striking differences in excretory behavior. While the initial excretory rates of the two groups seem comparable, the snails tested during the day seem to synthesize and excrete a smaller amount of ammonia than those tested at night. The effect of tide on rates of excretion remains to be determined. -15 Summary 1) Moisture appears to be a stimulus for ammonia excretion; since this nitrogenous waste product is water¬ soluble, ambient moisture would facilitate diffusion. 2) L. planaxis displays peaks of excretory activity which coincide with times of greatest moisture, i.e., night and high tide, thus maximizing opportunities for excretion. 3) Light and dark seem to be the strongest factors influencing this change in excretory activity; the tidal correlations become more apparent when normal light and dark cues are removed. 4) If deprived of moisture, L. planaxis excretes smaller amounts of ammonia; since this compound is toxic, ammonia synthesis could be harmful if no means were avail¬ able for excretion. 5) Rates of ammonia synthesis appear to be greater at night than during the day. Acknowledgements I would like to thank Dr. John H. Phillips for his insights, suggestions and encouraging winks. -16 Literature cited Campbell, J. W. and Bishop, S. H. (1970), Nitrogen meta¬ bolism in molluscs in Comparative Biochemistry of Nitrogen Metabolism, J. W. Campbell, ed., Academic Press, London and New York, Vol. I, pp. 103-206. A., (1964),An analysis of nitrogenous waste products Cox, in Littorina planaxis (unpublished manuscript on file at the Hopkins Marine Station Library, Pacific Grove, California.) Duerr, F., (1968), Excretion of ammonia and urea in seven species of marine prosobranch molluscs, Comp. Biochem. Physiol. 26:1051. E., (1964), The effect of certain environmental Kops, factors on the activity pattern of Littorina planaxis and Littorina scutulata (unpublished manuscript on file at the Hopkins Marine Station Library, Pacific Grove, California.) Lebenson, J., (1964), Respiration in Littorina planaxis and Littorina scutulata (unpublished manuscript on file at the Hopkins Marine Station Library, Pacific Grove, California.) Pederson, R. E., (1964) The lower limits of the habitats of Littorina scutulata and Littorina planaxis (unpub- lished manuscript on file at the Hopkins Marine Station Library, Pacific Grove, California.) Ternberg, J. L. and Hershey, F. B., (1964), Colorimetric determination of blood ammonia, J. Lab. and Clin. Med. 56:766-776. Figure 1: Amounts of ammonia excreted by samples of ten snails collected from the intertidal at the times indicated. The open circles repre¬ sent the mean values, the bars represent 95% confidence intervals and the closed circles represent the actual values of each of the samples. U9. NH79 3I 88586 8 • - • — — — kk — — tide sunsel sunrise Figure 2: Amounts of ammonia excreted by samples of ten snails kept in normal light conditions and periodically tested. The open circles repre¬ sent the mean values and the bars represent 95% confidence intervals. E9 NH/9 snail 8. 8 3 -e — — — — k k t- tide sundel sungise e Figure 3: Amounts of ammonia excreted by the individual groups of snails represented in Figure 2. Open circles at 1100 hours indicate the amounts ex¬ creted after twenty hours of dryness. (No data for groups 2 and 5 at 2200 hours., 10 00 O 5 00 10 0 — 00 o 10 —8 00 10 12 14 16 18 20 22 0 2 4 6 8 10 12 14 lime oi doy Figure 4: Amounts of ammonia excreted by samples of ten snails kept in normal light conditions and kept dry until time of testing. Open circles represent the mean values, bars represent the 95% confidence intervals and closed squares represent the actual values of each of the samples. 28 5 19 NH3/g snail 8 56 8 8 8 — — — k — k s fide unset) Munset Figure 5: Amounts of ammonia excreted by samples of ten snails kept in constant light or constant dark and periodically tested. Open circles represent the mean values and bars represent the 95% confidence intervals. 35 30 20 15 10 5 05 oo 35 o0 10 12 14 16 18 20 22 O 2 4 | 6 | 8 10 imeoday Figure 6: Amounts of ammonia excreted by the individual groups of snails represented in Figure 5. (No data for group 5 at 0600 hours, or for group 7 at 2330 hours.) . 2S 3 S 8 8 8 8 9 NH9 sni 88 tide sunset sunride sunsel sunrige 3L dnoib Figure 7: Amounts of ammonia excreted by samples of twenty snails at the int als indicate Open circles indicate the amount excreted by one sample group during the day. Open squares indicate the amount excreted by one sample group during the night. Pis a5 0 O time (hours)